CN114456669B

CN114456669B - Antibacterial and seaweed adhesion-resistant silane-modified polyampholyte hydrogel high-adhesion coating and preparation method thereof

Info

Publication number: CN114456669B
Application number: CN202210097535.XA
Authority: CN
Inventors: 李学锋; 商伶俐; 朱华雄; 黄以万; 陈梦繁; 王永林; 董鑫; 刘若卿
Original assignee: Hubei University of Technology
Current assignee: Hubei University of Technology
Priority date: 2022-01-27
Filing date: 2022-01-27
Publication date: 2022-12-02
Anticipated expiration: 2042-01-27
Also published as: CN114456669A

Abstract

The invention relates to a preparation method of a bacteriostatic and seaweed adhesion-resistant silane modified polyampholyte hydrogel high-adhesion coating. According to the invention, silane modified polyampholyte hydrogel is adopted, and the silane coupling effect and the ionic bond synergistic effect of the DAC molecular chain and the substrate enable the hydrogel coating to have excellent adhesive property, and meanwhile, the hydrogel coating has good antibacterial property and diatom adhesion resistance, can be used as a preferred material of a marine antifouling coating, and has a wide application prospect.

Description

Antibacterial and seaweed adhesion-resistant silane-modified polyampholyte hydrogel high-adhesion coating and preparation method thereof

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a silane modified polyampholyte hydrogel high-adhesion coating with bacteriostasis and seaweed adhesion resistance and a preparation method thereof.

Background

The hydrogel is a polymer with a three-dimensional network structure, can store a large amount of water without swelling and damage in water, can lock the water and maintain the stability of the structure, has the characteristics of smooth surface, lower surface energy and the like after absorbing the water, is similar to a mucus layer secreted by the body surface of a large marine organism, and has wide application prospect in the aspect of marine antifouling as a hydrogel coating. However, the general hydrogel has poor adhesion with a substrate material after absorbing water and swelling, cannot inhibit the growth of marine organisms, and cannot meet the use requirement, so that research is further developed into designing an adhesion-lubrication double-sided hydrogel coating which is firmly adhered with the substrate material and has the marine organism growth inhibition effect. To secure the adhesion of the hydrogel to the surface of the material, gong et al [ Gong, J.P., et al. (2018) ], "Tough partial-based double network hydrogels for functional surface coatings" -Advanced Materials Interfaces,2018,5 (23): 1801018.]By introducing initiator Benzophenone (BP) and polyvinyl acetate (PVAc) to the surface of the solid substrate, the BP is used as a grafting agent to initiate acrylamide (AAm) to form PAAm long chain, and simultaneously, covalent interaction is formed between the PVAc and the PAAm, and the synergistic effect of the two causes that the prepared hydrogel has strong bonding effect (more than 1000J/m) with the solid substrate in the process of debonding ² ). However, the method is complex to operate and difficult to become a common method for high-viscosity hydrogel, and reagents such as acetone and the like which are used in large quantities in the preparation process can cause certain pollution, thereby limiting the application prospect. On the other hand, the double network designed by the method contains a non-electrolyte polymer PAAm, and the weak hydration of the PAAm can cause that the gel is greatly limited in application due to the problems of biological pollution and the like. Xiong et al [ Xiong, L., et al. (2019). "connecting, tough, transparent,and Self-Healing Hydrogels Based on Catechol-Metal Ion Dual Self-Catalysis.”Chemistry of Materials,2019,31(15): 5625～5632.]A novel double-autocatalysis system based on a catechol-metal ion complex is designed, dopamine (DA), tannic Acid (TA), tea Polyphenol (TP) and the like and transition metal ions are utilized, ammonium Persulfate (APS) is activated efficiently and rapidly to generate free radicals, free radical polymerization of various vinyl monomers is triggered, and multifunctional hydrogel is generated. Because dynamic cross-linking points are effectively formed between the metal ions and the carboxyl and the catechol groups of the DA at the fracture interface of the hydrogel, the hydrogel obtained by the method has good self-healing capability, the hydrogel is cut into two pieces and then combined together, after healing is carried out for 6 hours, the tensile property of the hydrogel is recovered to 85 percent of the original tensile property, and the hydrogel still has good tensile property after self-healing. Although the method is simple to operate and avoids certain pollution caused by reagents in the preparation process, strong adhesion can be realized only by relying on a catechol structure of dopamine, and the catechol structure is easy to be converted into a quinoid structure to cause adhesion failure, so that the method is also greatly limited in practical application. Jiang et al [ Jiang, L., et al. (2018) ] "derived dictionary using a hydrogel with an organic acid as a targeted food" [ Journal of Materials Chemistry A,2018,6 (39): 19125-19132.]3-methacryloxypropyltrimethoxysilane is copolymerized and fixed in polyvinyl alcohol/polyacrylamide (PVA/PAAm) gel, the hydrogel is further hydrolyzed to obtain orthosilicic acid analogue (SOSA) with three silicon hydroxyl groups, and thus the flexible diatom attachment resistant hydrogel is prepared. However, the SOSA hydrogel prepared by the method also has the defects of weak hydration of a non-electrolyte type hydrophilic polymer PVA/PAAm network and weak bonding effect of the exposed silane on the surface of the hydrogel and a substrate.

Previous researches show that excellent bonding performance can be realized by forming a proper chemical bond between the hydrogel coating and the substrate, and the silane modified hydrogel coating not only can help to realize high bonding, but also can inhibit the growth of marine diatoms to a certain extent, so that the method is urgent and important research work.

Disclosure of Invention

The invention aims to solve the technical problems and provides a preparation method of a hydrogel high-adhesion coating, which is simple in process, easy to operate and control, easy to obtain raw materials, low in cost, short in period and antibacterial and seaweed adhesion resistant.

The technical scheme comprises the following specific steps:

a preparation method of a bacteriostatic and seaweed adhesion-resistant silane modified polyampholyte hydrogel high-adhesion coating comprises the following steps:

1) Adding DAC, naSS, a cross-linking agent and an initiator into deionized water, and stirring and dissolving to obtain a uniform prepolymer solution A;

2) Adding 3-methacryloxypropyltrimethoxysilane (MEMO) into the obtained prepolymer solution A, and uniformly mixing by ultrasonic to obtain a prepolymer solution B;

3) Carrying out hydroxylation treatment and silane treatment on the surface of a base material to be treated to obtain a pretreated base material;

4) And covering the surface of the pretreated base material with prepolymer solution B and forming a hydrogel coating to obtain the bacteriostatic and seaweed adhesion-resistant silane modified polyampholyte hydrogel high-adhesion coating.

Preferably, in the prepolymer solution a, the molar ratio of the monomers DAC to NaSS is 0.45: 0.55-0.5: 0.5.

preferably, the total concentration of DAC and NaSS in the prepolymer solution A is 2.337mol/L.

Preferably, the initiator is KA, accounting for 0.1 percent of the total mole amount of the monomers; the crosslinking agent is MBAA and accounts for 0.1 percent of the total mole amount of the monomers.

Preferably, the hydrogel coating is formed by placing the prepolymer solution B in a mold, and placing under an ultraviolet lamp for illumination under the following conditions: irradiating for 10-12 h under an ultraviolet lamp with the wavelength of 365nm and the power of 300W, removing the mould after forming, and swelling and balancing the obtained hydrogel coating in deionized water to obtain the Polyampholyte (PA) hydrogel coating.

Preferably, the mold consists of a base material, untreated glass and a silicone gasket, and is preheated by an oven before use at the temperature of 70-90 ℃ for 15-30 min.

Preferably, the volume ratio of the MEMO in the prepolymer solution B is 0.15-0.2%.

Preferably, the hydroxylation treatment process in the step 3) is as follows: washing the substrate with deionized water, drying, and carrying out plasma washing to obtain a hydroxylated substrate surface; the silane treatment process comprises the following steps: and uniformly mixing and stirring ethanol, acetic acid, deionized water and MEMO to obtain a mixed solution, soaking the hydroxylated base material in the obtained mixed solution, and drying to obtain the pretreated base material.

Preferably, in the mixed solution used for silane treatment, the ratio of acetic acid: water: volume ratio of ethanol =0.01:1:4,the content of MEMO with respect to the above mixed solution was 2% by weight.

Preferably, the plasma cleaning time is 10 to 30min during the hydroxylation treatment.

Preferably, in the silane treatment process, the soaking time of the substrate is 1-3 h, the drying time is 10-60 min, and the temperature during drying is controlled to be 50-80 ℃.

The invention also aims to provide the antibacterial and seaweed adhesion-resistant silane modified polyampholyte hydrogel high-adhesion coating which is prepared by the preparation method.

The invention prepares the 'bonding-lubricating double-sided' hydrogel coating through polyampholyte hydrogel. During the preparation process, trimethyl ammonium ions on DAC and sulfonate groups on NaSS form strong and weak ionic bonds which are uniformly and densely distributed in the interior of the polyampholyte hydrogel, and when the hydrogel coating swells and balances in deionized water, na is carried out along with the Na ⁺ And Cl ^- The hydrogel is continuously dialyzed, strong and weak ionic bonds are more and more stable, and the finally balanced hydrogel body has excellent mechanical properties. The energy dissipation of the hydrogel coating in the stripping process is divided into two parts of gel body destruction and interface destruction, at the interface, the silane primer for reaction is prepared by dehydration condensation between hydroxyl MEMO, the MEMO molecular chain contains silanol bonds, and can be chemically bonded with solids such as metal, glass, ceramic and the like with hydroxyl-rich surfaces, and the silane primer is arranged on the surface of a solid substrateThe surface forms a firm reactive silane primer. The amphoteric polyelectrolyte hydrogel coating is obtained by introducing a prepolymer solution formed by a cationic monomer DAC and an anionic monomer NaSS to the surface of the silane primer for copolymerization, and on one hand, because the DAC in the prepolymer solution is excessive and the DAC molecular chain contains free trimethyl ammonium ions, hydroxyl on the surface of the base material can form an ionic bond with the DAC molecular chain after deprotonation, so that chemical bonding is formed between the gel and the base material. On the other hand, in the process of hydrogel coating copolymerization, the MEMO adhered to the surface of the solid substrate is used as a coupling agent to form crosslinking with DAC and NaSS molecular chains, and strong adhesion is formed between the polyampholyte hydrogel and the solid substrate under the synergistic action of ionic bonds and silane coupling. The polyampholyte hydrogel coating prepared by the invention has the advantages of simple and easily-controlled preparation process, uniform structure of the prepared hydrogel coating, free forming, high strength, high toughness and the like while strong adhesion is obtained, and the method becomes a common method for preparing the high-viscosity hydrogel coating.

In addition, the polyampholyte hydrogel lubricating coating obtained by the invention has multi-scale antifouling capacity. On one hand, the PA/MEMO hydrogel coating has good protein adsorption resistance and can prevent the generation of a basement membrane in the marine pollution process. On the other hand, the PA/MEMO hydrogel coating can inhibit the growth of bacteria, and thus the formation of a biofilm. The DAC molecular chain in the hydrogel coating contains free trimethyl ammonium ions, and the free trimethyl ammonium ions can be combined with the surface of a negatively charged bacterial cell in the environment of gram-negative bacteria such as escherichia coli, so that the permeability of the cell membrane is changed, the cell component is leaked, and finally the bacteria die. In addition, the PA/MEMO hydrogel coating can also destroy the life activities of diatoms, and further prevent the growth of small and medium-sized fouling organisms in marine pollution. The MEMO is bifunctional organosilane with active mercapto group and hydrolysable methoxy group, as a silicic acid analogue synthesized by hydrolysis, and the structure of the MEMO is similar to that of orthosilicic acid required in the life process of diatom. Since the cell wall of diatom is SiO ₂ Cell wall, which is constructed by obtaining ortho silicic acid rich in seawater, when diatom settle inThe surface of the hydrogel coating can absorb the MEMO with a structure similar to that of orthosilicic acid indiscriminately, and the C-Si bond is relatively stable and cannot be condensed to form a silicon dioxide shell like orthosilicic acid, so that diatoms cannot normally construct cell walls after absorbing the MEMO, normal life activities of the diatoms are disordered and are finally stopped. Meanwhile, the polyampholyte hydrogel has extremely high ion group density, the free hydration energy (about-200 to-300 kJ/mol) of the zwitterionic group is lower than that (about-100 to-200 kJ/mol) of the nonionic hydrophilic polymer, and the polyampholyte hydrogel has stronger affinity and hydrophilicity with water, so that a compact hydration layer is formed on the surface of the gel very easily. And the polyampholyte hydrogel is wholly neutral, and overcomes the defects of low mechanical property caused by strong charge adsorption and high swelling degree of the general cationic polyelectrolyte or anionic polyelectrolyte hydrogel. The formation of high hydration layers on polyampholyte hydrogels can also inhibit the adhesion of marine organisms on the hydrogel coating, ultimately affecting the adhesion behavior of diatoms. The incorporation of the MEMO in conjunction with the good lubricity of the PA hydrogel itself may result in a PA/MEMO hydrogel coating having excellent diatom adhesion resistance.

Compared with the prior art, the invention has the following advantages and remarkable progress:

1) The invention has the advantages of simple preparation process, good controllability, simple and convenient process conditions, easy repetition, low production cost, easily obtained raw materials and stable product performance.

2) The method is different from the mode of achieving bacteriostasis and diatom adhesion resistance through micromolecule adsorption and release, adopts silane modified polyampholyte hydrogel, and enables the hydrogel coating to have excellent adhesive property through the coupling effect of silane and the synergistic effect of ionic bonds of DAC molecular chains and a substrate. Meanwhile, due to the existence of cations on DAC molecular chains and MEMO in a system, the hydrogel coating has good antibacterial performance and diatom adhesion resistance, can be used as a preferred material of a marine antifouling coating, and has wide application prospects.

Drawings

FIG. 1 is a schematic diagram of the design principle of a silane-modified polyampholyte hydrogel coating;

FIG. 2 is a comparison graph of the bacteriostatic properties of the PA and P-DN hydrogels, wherein the upper and lower parts are respectively the pictures of the bacteriostatic circle of the PA and P-DN hydrogels and the electron microscope observation pictures of Escherichia coli on the corresponding surfaces;

FIG. 3 is a graph comparing the diatom-stick resistance of PA and PA/MEMO hydrogels, wherein the left graph is a graph of the diatom-stick resistance of the PA hydrogel and the right graph is a graph of the diatom-stick resistance of the PA/MEMO hydrogel.

Detailed Description

Testing the bonding performance of the hydrogel coating and the solid substrate:

example 1

Step 1): and (3) carrying out plasma cleaning on the glass substrate which is cleaned and dried by the deionized water for 10min to obtain the hydroxylated substrate surface.

Step 2): 80ml of ethanol, 20ml of deionized water and 0.2ml of acetic acid are respectively weighed into a tetragonal container, and are uniformly mixed after 2wt% of MEMO relative to the mass of the solvent is added.

Step 3): putting the glass substrate in the step 1) into the mixed solution in the step 2), dip-coating for 2 hours at room temperature, and drying for 30min at 60 ℃.

Step 4): and (3) forming a mould by the glass substrate obtained in the step 3), untreated glass and a silicone gasket, and preheating for 30min in a 90 ℃ oven.

Step 5): 3.1122g of DAC (55 mol%), 2.4093g of NaSS (45 mol%), 0.0039g of MBAA (0.1 mol%) and 0.0037g of KA (0.1 mol%) were weighed out separately in a beaker, 10ml of deionized water was added and stirred in a 70 ℃ water bath for 15min to obtain a uniform prepolymer solution.

Step 6): adding 15 mu l of MEMO into the prepolymer solution obtained in the step 5), uniformly mixing by ultrasonic waves, transferring the mixture into the mold in the step 4), irradiating the mixture for 10 hours under an ultraviolet lamp, removing untreated glass and a silicone gasket to obtain a pre-polymerized PA/MEMO hydrogel coating, and swelling and balancing the pre-polymerized PA/MEMO hydrogel coating in deionized water to obtain the PA/MEMO hydrogel coating.

Correspondingly, preparing PA/MEMO hydrogel sample: except that the plasma treatment and the MEMO solution treatment of the mould in the steps 1, 2 and 3 are not adopted and then the mould is dried, the PA/MEMO hydrogel sample wafer can be obtained by other steps.

Example 2

Step 1): and plasma cleaning the glass substrate which is cleaned and dried by the deionized water for 10min to obtain the hydroxylated substrate surface.

Step 2): 80ml of ethanol, 20ml of deionized water and 0.2ml of acetic acid are respectively weighed and put in a tetragonal container, 2wt% of MEMO is added and then the mixture is uniformly mixed.

Step 5): 2.9055g of DAC (51.33 mol%), 2.6062g of NaSS (48.66 mol%), 0.0039g of MBAA (0.1 mol%) and 0.0037g of KA (0.1 mol%) are respectively weighed in a beaker, 10ml of deionized water is added, and then the mixture is stirred in a water bath at 70 ℃ for 15min to obtain a uniform prepolymer solution.

Step 6): adding 19 mu.l of MEMO into the prepolymer solution obtained in the step 5), uniformly mixing by ultrasonic waves, transferring the mixture into the mold in the step 4), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and a silicone gasket to obtain a pre-polymerized PA/MEMO hydrogel coating, and swelling and balancing the pre-polymerized PA/MEMO hydrogel coating in deionized water to obtain the PA/MEMO hydrogel coating.

Example 3

Step 4): and (4) forming a mould by the glass substrate obtained in the step 3), untreated glass and a silicone gasket, and preheating in an oven at 90 ℃ for 30min.

Step 5): 2.8292g of DAC (50 mol%), 2.677g of NaSS (50 mol%), 0.0039g of MBAA (0.1 mol%) and 0.0037g of KA (0.1 mol%) were weighed into a beaker, 10ml of deionized water was added, and the mixture was stirred in a 70 ℃ water bath for 15min to obtain a uniform prepolymer solution.

Step 6): adding 20 mu.l of MEMO into the prepolymer solution obtained in the step 5), uniformly mixing by ultrasonic waves, transferring the mixture into the mold in the step 4), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and a silicone gasket to obtain a pre-polymerized PA/MEMO hydrogel coating, and swelling and balancing the pre-polymerized PA/MEMO hydrogel coating in deionized water to obtain the PA/MEMO hydrogel coating.

Correspondingly, preparing a PA/MEMO hydrogel sample: except that the mould is not treated by plasma and the MEMO solution in the steps 1, 2 and 3 and then dried, the PA/MEMO hydrogel sample can be obtained by the other steps.

Comparative example 1

Step 2): forming a mould by the glass substrate obtained in the step 1), untreated glass and a silicone gasket, and preheating for 30min in a 90 ℃ oven.

Step 3): 2.9055g of DAC (51.33 mol%), 2.6062g of NaSS (48.66 mol%), 0.0039g of MBAA (0.1 mol%) and 0.0037g of KA (0.1 mol%) are respectively weighed in a beaker, 10ml of deionized water is added, and then the mixture is stirred in a water bath at 70 ℃ for 15min to obtain a uniform prepolymer solution.

Step 4): transferring the prepolymer solution in the step 3) into the mold in the step 2), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and silicone gaskets to obtain a pre-polymerized PA hydrogel coating, and swelling and balancing the pre-polymerized PA hydrogel coating in deionized water to obtain the PA hydrogel coating.

Correspondingly, preparation of a PA hydrogel sample: except that the plasma treatment of the mold in the step 1 is not adopted, the PA hydrogel sample wafer can be obtained by the other steps.

Comparative example 2

Step 2): and (2) forming a mould by the glass substrate obtained in the step 1), untreated glass and a silicone gasket.

And step 3): 5.6864g of acrylamide (4 mol/l), 0.3g of PNAAMPS (15 mg/ml), 0.0012g of MBAA (0.01 mol%) and 0.0011g of KA (0.01 mol%) are respectively weighed into a beaker, 10ml of deionized water is added, and the mixture is stirred and dissolved at room temperature to obtain a uniform prepolymer solution.

And step 4): and (3) transferring the prepolymer solution in the step 3) into the die in the step 2), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and silicone gaskets to obtain a prepolymerized microgel enhanced hydrogel (P-DN) coating, and swelling and balancing the coating in deionized water to obtain the P-DN hydrogel coating.

Correspondingly, preparing a P-DN hydrogel sample: except that the plasma treatment of the mold in the step 1 is not adopted, the P-DN hydrogel sample wafer can be obtained by the other steps.

Comparative example 3

Step 4): adding 19 mu.l of MEMO into the prepolymer solution in the step 3), uniformly mixing by ultrasonic waves, transferring the mixture into the mold in the step 2), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and a silicone gasket to obtain a pre-polymerized P-DN/MEMO coating, and swelling and balancing the pre-polymerized P-DN/MEMO coating in deionized water to obtain the P-DN/MEMO hydrogel coating.

Correspondingly, preparing a P-DN/MEMO hydrogel sample: except that the plasma treatment of the mold in the step 1 is not adopted, the P-DN/MEMO hydrogel sample can be obtained by the same steps.

Comparative example 4

Step 3): 5.6585g (2.337M) of DAC, 0.0039g of MBAA (0.1 mol%) and 0.0037g of KA (0.1 mol%) were weighed into a beaker, and 10ml of deionized water was added thereto, followed by stirring in a 70 ℃ water bath for 15min to obtain a uniform prepolymer solution.

And step 4): transferring the prepolymer solution in the step 3) into the mold in the step 2), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and silicone gaskets to obtain a pre-polymerized PDAC hydrogel coating, and swelling and balancing the pre-polymerized PDAC hydrogel coating in deionized water to obtain the PDAC hydrogel coating.

Correspondingly, preparing a PDAC hydrogel sample: except that the plasma treatment of the mold in the step 1 was not used, a sample piece of PDAC hydrogel was obtained in the same manner as above.

Comparative example 5

Step 3): 5.3541g (2.337M) NaSS, 0.0039g MBAA (0.1 mol%) and 0.0037g KA (0.1 mol%) were weighed into a beaker, 10ml deionized water was added, and the mixture was stirred in a 70 ℃ water bath for 15min to obtain a uniform prepolymer solution.

Step 4): transferring the prepolymer solution A in the step 3) into the mold in the step 2), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and silicone gaskets to obtain a pre-polymerized PNaSS hydrogel coating, and swelling and balancing the pre-polymerized PNaSS hydrogel coating in deionized water to obtain the PNaSS hydrogel coating.

Correspondingly, preparing a PNaSS hydrogel sample: except that the plasma treatment of the mold in the step 1 is not adopted, the PNaSS hydrogel sample wafer can be obtained by the other steps.

Comparative example 6

Step 3): 11.3728g of AAm (8 mol/l), 0.0012g of MBAA (0.01 mol%) and 0.0011g of KA (0.01 mol%) are respectively weighed into a beaker, 10ml of deionized water is respectively added, and the mixture is stirred and dissolved at room temperature to obtain a uniform prepolymer solution.

And step 4): transferring the prepolymer solution in the step 3) into the mold in the step 2), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and silicone gaskets to obtain a pre-polymerized PAAm hydrogel coating, and swelling and balancing the pre-polymerized PAAm hydrogel coating in deionized water to obtain the PAAm hydrogel coating.

Correspondingly, PAAm hydrogel sample preparation: except that the plasma treatment of the mould in the step 1 is not adopted, the PAAm hydrogel sample wafer can be obtained by other steps.

Comparative example 7

And step 3): 16,58g NaAMPS (8 mol/l), 0.0012g MBAA (0.01 mol%) and 0.0011g KA (0.01 mol%) are respectively weighed into a beaker, 10ml deionized water is respectively added, and the mixture is stirred and dissolved at room temperature to obtain a uniform prepolymer solution.

Step 4): transferring the prepolymer solution in the step 3) into the mold in the step 2), irradiating for 10 hours under an ultraviolet lamp, removing untreated glass and silicone gaskets to obtain a pre-polymerized PNAAMPS hydrogel coating, and swelling and balancing the PNAAMPS hydrogel coating in deionized water to obtain the PNAAMPS hydrogel coating.

Correspondingly, preparation of PNaAMPS hydrogel sample: except that the plasma treatment of the mold in the step 1 is not adopted, the PNaAMPS hydrogel sample wafer can be obtained by the same steps as above.

Protein adhesion test:

step 1): the hydrogel was equilibrated by soaking in 0.1M Phosphate Buffered Saline (PBS) pH 7.4 for 24h at 37 ℃.

Step 2): after cutting the gel in step 1) into discs with the diameter of 11mm, the discs are soaked in 15ml of 1mg/ml BSA solution (solvent 0.1M PBS solution with pH 7.4), weighed and then subjected to adsorption equilibrium at 37 ℃ for 24h.

Step 3): the sample after adsorption equilibrium was supplemented with a weight and the UV absorbance of the solution at 595nm was measured by Coomassie Brilliant blue.

And step 4): calculating the adsorption quantity of the hydrogel to the bovine serum albumin by using a standard curve and a formula (1):

wherein, C ₀ Is the initial concentration of BSA solution, C _i Is the concentration of BSA solution after adsorption, m _i And S _i Is the mass and water content of the hydrogel sample after adsorption, and V is the volume of the solution.

And (3) testing bacteriostatic performance:

step 1): weighing 1g of peptone, 0.5g of yeast powder, 1g of NaCl and 1.5g of agar powder respectively in a conical flask, uniformly mixing, sealing with a cotton plug, and sterilizing in an autoclave for 2 times, 2 hours each time.

Step 2): sterilizing the culture dish in a fume hood by ultraviolet rays for 20min, pouring the liquid obtained in the step 1) into the culture dish while the liquid is hot, and cooling and air-drying for 15min to obtain a solid culture medium, wherein the operations are carried out in a sterile fume hood.

Step 3): and (3) putting 30 mu l of escherichia coli bacterial liquid on the solid culture medium in the step 2), and carrying out flat plate coating by using a glass propeller after burning and cooling to obtain the solid culture medium containing the bacterial liquid.

And step 4): flatly placing a hydrogel sample with the surface drying and the diameter of 11mm on the solid culture medium obtained in the step 3), covering a culture dish, inverting, sealing with a preservative film, and then culturing for 12 hours in a shaking table at the constant temperature of 37 ℃ to observe whether a bacteriostatic zone is formed.

Step 5): adding 2.5wt% of glutaraldehyde into PBS with the pH of 7.4, and soaking and fixing the hydrogel cultured in the solid culture medium for 12 hours in the step 4) for 2 hours to obtain a treated hydrogel sample.

Step 6): soaking the sample obtained in the step 5) in 10wt%, 30wt%, 50wt%, 70wt% and 90wt% ethanol solutions for 20min, soaking in ethanol twice for 20min each time, further freeze-drying for 24h, spraying gold, and performing a scanning electron microscope observation experiment.

Resistance to diatom adhesion test:

step 1): the hydrogel samples prepared were cut into squares of 2cm by 2 cm.

Step 2): putting 100ml of navicula suspension into a beaker, putting the hydrogel sample obtained in the step 1) into the beaker, culturing the hydrogel sample under illumination for 12h at 25 ℃, then culturing the hydrogel sample in the dark for 12h, taking out the hydrogel sample, washing out navicula unadhered on the surface, placing the hydrogel sample on a glass sheet, and observing the adhesion condition of diatoms on the surface of the gel under a fluorescence microscope.

The hydrogel sample sheets of examples 1 to 3 and comparative examples 1 to 3 were subjected to a tensile test, the hydrogel coating was subjected to a 90 ° peel test, the hydrogel sample sheets of comparative examples 4 to 7 were subjected to a compression test, and the hydrogel coating was subjected to a 90 ° peel test, and the tensile/compressive strength, elongation at break/compression ratio, and adhesive strength of each product were as follows:

table 1: tensile strength and adhesive strength of hydrogel coatings

Note: examples 1 to 3 and comparative examples 1 to 3 are hydrogel tensile strength, and comparative examples 4 to 7 are extremely low in tensile strength and tested for compressive strength.

As can be seen from the data in the table:

examples 1-3 are PA/MEMO hydrogel coatings prepared with varying molar ratios of DAC and NaSS, volume content of MEMO, comparative examples 1-3 are PA hydrogel coatings, P-DN hydrogel coatings and P-DN/MEMO hydrogel coatings prepared, and comparative examples 4-7 are PDAC, PNaSS, PAAm and PNaAMPS single network hydrogel coatings prepared. As can be seen from examples 1 to 3 and comparative example 1, the bulk mechanical strength of the hydrogel was slightly reduced with the introduction of the MEMO, but at the same time, the adhesion strength between the hydrogel and the substrate was from 413J/m ² Enhanced to 1038J/m ² It is known that the synergistic effect of ionic bonding and silane coupling results in hydrogel coatings with excellent adhesive strength. Comparative example 1 only the glass substrate was subjected to hydroxylation treatment, the adhesion strength of the obtained coating was much lower than that of examples 1 to 3, and the hydrogel coatings obtained in comparative examples 2 to 7 also peeled off directly. The above results demonstrate that by introducing the MEMO into the PA hydrogel coating system, both ionic bonds and silane coupling can be combined to form a significant synergistic effect, giving the hydrogel coating excellent adhesion properties.

The hydrogels of examples 1 to 3 and comparative examples 1 to 7 were subjected to a protein adsorption resistance test, and the protein adsorption amounts of the respective products are shown in Table 2 below:

the protein adsorption of the hydrogels of the above examples and comparative examples is shown in table 2 below:

table 2: protein adsorption behavior of hydrogels

As can be seen from the data in table 2:

examples 1 to 3, comparative example 1 and comparative example 7 all had better protein adsorption resistance. Protein is a substance with electric charge, and the electric adsorption property of the protein enables cationic or anionic polyelectrolyte gel to easily adsorb protein, so that the overall neutral polyamphiphilic electrolyte has the advantage of resisting protein adsorption from the viewpoint of electric charge adsorption. The protein diffusion and absorption of the hydrogel depends on the protein charge, the gel charge density and the solution ionic strength, the BSA selected for the test of the invention has negative charge, the BSA is more prone to be adsorbed on the hydrogel with positive charge, and the electrostatic interaction between the hydrogel and the BSA dominates the protein diffusion and absorption of the hydrogel. The coordination use of NaSS and DAC in the PA hydrogel obtained by the invention enables the hydrogel system to approach the isoelectric point, and the whole free positive charge of the hydrogel is very little, so that the embodiment hydrogel and the comparative example hydrogel have less adsorption quantity to BSA (bovine serum albumin), and have better protein adsorption resistance. Similarly, comparative example 7 is a PNaAMPS negative charge hydrogel, which also has good protein adsorption resistance, while comparative example 4 is a PDAC positive charge hydrogel, which can adsorb a large amount of protein. The results show that the polyelectrolyte hydrogel has good protein adsorption resistance, so that the hydrogel coating has good antifouling effect.

The hydrogel in examples 1-3 and comparative examples 1-7 was tested for bacteriostatic performance, and the bacteriostatic condition of each product is shown in table 3 below:

the hydrogel for the above examples and comparative examples has the following bacteriostatic effect in table 3:

table 3: bacteriostatic behavior of hydrogels

As can be seen from the data in table 3:

examples 1 to 3 and comparative example 1 all had good bacteriostatic properties. Comparative example 4 also had a smaller colony area on the surface than the other comparative examples. In contrast, in comparative examples 2, 3 and 5 to 7, the hydrogel molecular chains have no large amount of free cations and have weak interaction with bacterial cell membranes, so that a large amount of Escherichia coli colonies appear on the hydrogel surface after culturing for 12 hours in a shaker at 37 ℃. This demonstrates that the PA hydrogel can provide good bacteriostatic properties to the hydrogel coating, and the introduction of the MEMO does not affect its bacteriostatic effect.

The hydrogels of examples 1-3 and comparative examples 1-7 were tested for resistance to diatom adhesion, and the products were shown in Table 4 below:

the hydrogels of the above examples and comparative examples have the following resistance to adhesion of diatoms as shown in table 4 below:

table 4: resistance of hydrogels to diatom adhesion

As can be seen from the data in table 4:

the hydrogel surfaces of examples 1-3 had much smaller areas resistant to diatom adhesion than those of comparative examples 1-7. The PA hydrogel and the P-DN hydrogel can form compact hydrated layers on the surfaces, have the effect of inhibiting marine organism adhesion, and the good hydration effect of the hydrogels is helpful for improving the diatom-resistant adhesion performance of the hydrogels as can be seen from the comparison of comparative examples 1 and 2 and comparative examples 4-7. However, after the MEMO is introduced, the PA and P-DN system hydrogel shows more excellent seaweed adhesion resistance. Among them, from the comparison between examples 1 to 3 and comparative example 3, it can be seen that PA/MEMO is significantly superior to P-DN/MEMO hydrogel in anti-diatom adhesion performance, indicating that introduction of MEMO and PA hydrogel itself generate a synergistic effect to make hydrogel coating have excellent anti-diatom adhesion performance.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A preparation method of a bacteriostatic and seaweed adhesion-resistant silane modified polyampholyte hydrogel high-adhesion coating is characterized by comprising the following steps:

1) Adding acryloyloxyethyl trimethyl ammonium chloride (DAC), sodium styrene sulfonate (NaSS), a cross-linking agent and an initiator into deionized water, and stirring and dissolving to obtain a uniform prepolymer solution A, wherein in the prepolymer solution A, the molar ratio of the DAC to the NaSS is (0.45: 0.55 - (0.5: 0.5 The total concentration of DAC and NaSS is 2.337 mol/L;

2) Adding 3-methacryloxypropyltrimethoxysilane (MEMO) into the obtained prepolymer solution A, and uniformly mixing by ultrasonic to obtain a prepolymer solution B, wherein the volume percentage of the MEMO in the prepolymer solution B is 0.15-0.2%;

3) Carrying out hydroxylation treatment and silane treatment on the surface of a base material to obtain a pretreated base material; the silane treatment process comprises the following steps: uniformly mixing and stirring ethanol, acetic acid, deionized water and MEMO to obtain a mixed solution, soaking the hydroxylated base material in the obtained mixed solution, and drying to obtain a pretreated base material; in the mixed solution used for silane treatment, acetic acid: water: volume ratio of ethanol =0.01:1:4,the content of the MEMO with respect to the mixed solution was 2 wt%;

2. The method of claim 1, wherein the initiator is 2-oxoglutarate (KA) in an amount of 0.1% by mole based on the total amount of the monomers; the crosslinking agent is N' N-Methylene Bisacrylamide (MBAA) and accounts for 0.1 percent of the total mole amount of the monomers.

3. The method of claim 1, wherein the hydroxylation process in step 3) is: and washing the substrate by deionized water, drying and carrying out plasma washing to obtain the hydroxylated substrate surface.

4. The method according to claim 3, wherein the plasma cleaning time is 10 to 30min during the hydroxylation treatment.

5. The preparation method according to claim 1, wherein in the silane treatment process, the soaking time of the substrate is 1 to 3 hours, the drying time is 10 to 60 minutes, and the temperature during drying is controlled to be 50 to 80 ℃.

6. A bacteriostatic and seaweed adhesion-resistant silane-modified polyampholyte hydrogel high-adhesion coating is characterized by being prepared by the preparation method of any one of claims 1-5.